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Investigation of Novel Metal Gate and High-κ Dielectric Materials for CMOS TechnologiesWestlinder, Jörgen January 2004 (has links)
The demands for faster, smaller, and less expensive electronic equipments are basically the driving forces for improving the speed and increasing the packing density of microelectronic components. Down-scaling of the devices is the principal method to realize these requests. For future CMOS devices, new materials are required in the transistor structure to enable further scaling and improve the transistor performance. This thesis focuses on novel metal gate and high-κ dielectric materials for future CMOS technologies. Specifically, TiN and ZrN gate electrode materials were studied with respect to work function and thermal stability. High work function, suitable for pMOS transistors, was extracted from both C-V and I-V measurements for PVD and ALD TiN in TiN/SiO2/Si MOS capacitor structures. ZrNx/SiO2/Si MOS capacitors exhibited n-type work function when the low-resistivity ZrNx was deposited at low nitrogen gas flow. Further, variable work function by 0.6 eV was achieved by reactive sputter depositing TiNx or ZrNx at various nitrogen gas flow. Both metal-nitride systems demonstrate a shift in work function after RTP annealing, which is discussed in terms of Fermi level pinning due to extrinsic interface states. Still, the materials are promising in a gate last process as well as show potential as complementary gate electrodes. The dielectric constant of as-deposited (Ta2O5)1-x(TiO2)x thin films is around 22, whereas that of AlN is about 10. The latter is not dependent on the degree of crystallinity or on the measurement frequency up to 10 GHz. Both dielectrics exhibit characteristics appropriate for integrated capacitors. Finally, utilization of novel materials were demonstrated in strained SiGe surface-channel pMOSFETs with an ALD TiN/Al2O3 gate stack. The transistors were characterized with standard I-V, charge pumping, and low-frequency noise measurements. Correlation between the mobility and the oxide charge was found. Improved transistor performance was achieved by conducting low-temperature water vapor annealing, which reduced the negative charge in the Al2O3.
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Obten??o de p?s de t?ntalo met?lico a partir da redu??o aluminot?rmica com igni??o a plasmaBrito, Roseane Aparecida de 26 March 2007 (has links)
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Previous issue date: 2007-03-26 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Metallic tantalum has a high commercial value due to intrinsic properties like excellent ductility, corrosion resistance, high melt and boiling points and good electrical and thermal conductivities. Nowadays, it is mostly used in the manufacture of capacitors, due to excellent dielectric properties of its oxides. In the nature, tantalum occurs in the form of oxide and it is extracted mainly from tantalite-columbite ores. The tantalum is usually produced by the reduction of its oxide, using reductants like carbon, silicon, calcium, magnesium and aluminum. Among these techniques, the aluminothermic reduction has been used as the industrial method to produce niobium, tantalum and their alloys, due to the easy removal of the Al and Al2O3 of the system, easing further refining. In conventional aluminothermic reduction an electrical resistance is used to trigger the reaction. This reaction self-propagates for all the volume of material. In this work, we have developed a novel technique of aluminothermic reduction that uses the hydrogen plasma to trigger the reaction. The results obtained by XRD, SEM and EDS show that is possible to obtain a compound rich in tantalum through this technique of aluminothermic reduction in the plasma reactor / O t?ntalo ? um metal de elevado valor comercial devido suas propriedades intr?nsecas como excelente ductilidade, resist?ncia ? corros?o, elevados pontos de fus?o e ebuli??o e boas condutividades t?rmica e el?trica. Atualmente sua maior aplica??o tem sido na produ??o de capacitores, devido ?s excelentes propriedades diel?tricas de seus ?xidos. Na natureza o t?ntalo ocorre na forma de ?xido e ? extra?do principalmente do min?rio tantalita-columbita. O p? de t?ntalo met?lico ? normalmente produzido pela redu??o do seu ?xido, utilizando agentes redutores tais como carbono, sil?cio, c?lcio, magn?sio e o alum?nio. Dentre estas t?cnicas, a aluminotermia vem sendo utilizada como m?todo industrial para a produ??o do ni?bio, t?ntalo e suas ligas, em virtude da f?cil remo??o do alum?nio (Al) e da alumina (Al2O3) do sistema, o que facilita a etapa de refino. No processo de aluminotermia convencional ? utilizado um elemento resistivo como ignitor da rea??o, que se auto-propaga para todo o volume de material. No presente trabalho foi desenvolvida uma t?cnica de aluminotermia que utiliza o plasma de hidrog?nio como ignitor da rea??o. Os resultados obtidos por DRX, MEV e EDS mostram que ? poss?vel a obten??o de um concentrado rico em t?ntalo pela t?cnica de redu??o aluminot?rmica a plasma
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Reliability and processing of ferroelectric thin film capacitors with emphasis on fatigue and etchingVijay, Dilip P. 06 June 2008 (has links)
Ferroelectric materials are characterized by a reversible spontaneous polarization in the absence of an electric field. The characteristic polarization response of a ferroelectric material to an applied electric field enables a binary state device in the form of a thin film ferroelectric capacitor that can be used to store digital information. This provides opportunities for the development of high speed, low cost and low power, nonvolatile memory devices. The development of commercial ferroelectric memory devices has however been hampered by (a) several reliability issues including fatigue, leakage current, aging, time dependent dielectric breakdown, retention and imprint and (b) processing problems including the development of a low temperature thin film deposition process and the development of a patterning technology.
Lead zirconate titanate (PZT) is now widely considered as the most promising material for ferroelectric memory applications as a result of its excellent ferroelectric properties and wide operating temperature range. However, it is commonly found that metal electroded-PZT capacitors (e.g., Pt/PZT/Pt) show a loss of switchable polarization with cumulative switching cycles. This phenomenon is known as fatigue and is the one of the critical problems affecting the lifetime of ferroelectric memories.
This research is primarily focused on the problem of fatigue. On the basis of a quantitative model, various guidelines to minimize the degradation problem have been derived. The model attributes fatigue to domain pinning by space charge that is caused by defect (e.g. oxygen vacancy) entrapment at various interface sites such as electrode-ferroelectric interface, domain boundaries and grain boundaries. Two different approaches to minimize the problem have been outlined : (a) control of the defect density and (b) control of the interface state. The control of interface state was achieved by replacing the metal electrodes with conducting oxide electrodes such as RuO₂. The oxide electrode/PZT capacitors were characterized for their diffusion barrier properties, perovskite phase formation, interface nature and ferroelectric properties. The results indicate that these oxide electroded PZT films are good candidates for nonvolatile memory applications. However, the leakage current levels at the operating voltages are far higher than the metal counterparts. Simultaneous minimization of fatigue and leakage current in PZT films was achieved by using multilayer metal/conducting oxide electrodes (e.g., Pt/RuO₂).
The control of defect density was attained by (a) donor doping to compensate for the oxygen vacancies (e.g, Nb doping in PZT) and (b) utilizing ferroelectric materials that have a low intrinsic defect concentration. As a result of the latter approach, novel ferroelectric materials belonging to the layer-structure family of oxides have been identified as excellent candidates for fatigue free nonvolatile memory applications. Laser ablated SrBi₂(Ta<sub>x</sub>Nb<sub>1 - x</sub>)₂O₉ (0<x<1) films showed very good hysteresis characteristics (remnant polarization value of 11 µC/cm², coercive field of 60 kV/cm), no fatigue was observed up to 10⁹ switching cycles and very low leakage current densities. Furthermore, the formation and properties of these films were characterized. It was found grain size and orientation played a major role in determining the properties of these films. C-axis oriented films were found to exhibit almost no polarization.
An additional objective of this research was to identify an etching technology (process integration issue) for patterning of the ferroelectric capacitors. The etching process should provide high etch rates, good etch anisotropy, high etch selectivity and minimal post etch residues. It has been shown that a reactive ion etch process with CCl₂F₂/O₂ as the etch gas mixture can meet these requirements. A detailed process study has been conducted to determine the mechanism of etching. / Ph. D.
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Employing Metal Iodides and Oxygen in ALD and CVD of Functional Metal OxidesSundqvist, Jonas January 2003 (has links)
<p>Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy.</p><p>This thesis describes atomic layer deposition of Ta<sub>2</sub>O<sub>5</sub>, HfO<sub>2</sub> and SnO<sub>2</sub> thin films and chemical vapour deposition of SnO<sub>2</sub> thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined.</p><p>The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.</p>
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Employing Metal Iodides and Oxygen in ALD and CVD of Functional Metal OxidesSundqvist, Jonas January 2003 (has links)
Many materials exhibit interesting and novel properties when prepared as thin films. Thin film metal oxides have had an impact on the technological progress of the microelectronics mainly due to their electrical and optical properties. Since the future goes towards the nanometre scale there is an increasing demand for thin film deposition processes that can produce high quality metal oxide films in this scale with high accuracy. This thesis describes atomic layer deposition of Ta2O5, HfO2 and SnO2 thin films and chemical vapour deposition of SnO2 thin films. The films have been deposited by employing metal iodides and oxygen as precursors. All these processes have been characterised with regards to important processing parameters. The films themselves have been characterised by standard thin film analysing techniques such as x-ray diffraction, scanning electron microscopy, atomic force microscopy and transmission electron microscopy. The chemical and physical properties have been coupled to critical deposition parameters. Furthermore, additional data in the form of electrical and gas sensing properties important to future applications in the field of microelectronics have been examined. The results from the investigated processes have shown the power of the metal iodide based atomic layer deposition (ALD) and chemical vapour deposition (CVD) processes in producing high quality metal oxide thin films. Generally no precursor contaminations have been observed. In contrast to metal chloride based processes the metal iodide processes produces films with a higher degree of crystalline quality when it comes to phase purity, roughness and epitaxy. The use of oxygen as oxidising precursor allowed depositions at higher temperatures than normally employed in water based ALD processes and hence a higher growth rate for epitaxial growth was possible.
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Estudo sobre a redu??o aluminot?rmica de Ta2O5 e TiO2 usando descarga de c?todo ocoBrito, Roseane Aparecida de 29 April 2011 (has links)
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Previous issue date: 2011-04-29 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / In this study it was used two metallic oxides, Ta2O5 and TiO2, in order to obtain
metallic powders of Ta and Ti through aluminothermic reduction ignited by plasma. Ta2O5
and TiO2 powders were mixed with Al in a planetary mill, using different milling times. A
thermal analysis study (DTA and TG) was carried out, in order to know the temperature to
react both the mixtures. Then, these mixtures were submitted to a hollow cathode discharge,
where they were reacted using aluminothermic reduction ignited by plasma. The product
obtained was characterized by XRD and SEM, where it was proven the possibility of
producing these metallic particles, different from the conventional process, where metallic
ingots are obtained. It was verified that the aluminothermic reduction ignited by plasma is
able to produce metallic powders of Ta and Ti, and a higher efficiency was observed to the
process with Ta2O5-Al mixtures. Among different microstructural aspects observed, it can be
noted the presence of metallic nanoparticles trapped into an Al2O3 matrix, besides acicular
structures (titanium) and dendritic structures (tantalum), which are a product characteristic
from a fast cooling / No presente estudo foram utilizados dois ?xidos met?licos, Ta2O5 e TiO2, visando a
obten??o de part?culas de Ta e Ti met?licos, por meio da redu??o aluminot?rmica com igni??o
a plasma. P?s de Ta2O5 e TiO2 foram misturados com p? de Al e mo?dos em um moinho
planet?rio por diferentes per?odos. Um estudo de an?lise t?rmica (DTA e TG) foi realizado,
visando se conhecer a temperatura de rea??o para ambas as misturas. Conhecidas essas
temperaturas, as misturas foram submetidas a uma descarga em c?todo oco, onde foram
reagidas pelo processo de redu??o aluminot?rmica com igni??o a plasma. O material obtido
foi caracterizado por DRX e MEV, onde se comprovou a possibilidade da obten??o de um
produto na forma de p?, algumas vezes de dimens?es nanom?tricas, diferentemente do
processo convencional, onde o produto final ? obtido na forma de lingote. Verificou-se que a
redu??o aluminot?rmica com igni??o a plasma ? capaz de produzir p?s de Ta e Ti met?licos,
com uma efici?ncia maior para a rea??o da mistura Ta2O5-Al. Dentre os diferentes aspectos
microestruturais observados, destaca-se a presen?a de nanopart?culas do metal de interesse
embebidas em uma matriz de Al2O3, al?m de estruturas acicular (tit?nio) e dendr?tica
(t?ntalo), que s?o caracter?sticas de um resfriamento r?pido
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Dielektrické vlastnosti tenkých vrstev oxidů niobu a tantalu / Dielectric Properties of Thin Tantalum and Niobium Oxide LayersAbuetwirat, Inas Faisel January 2014 (has links)
Dielektrická relaxační spektroskopie je jednou z užitečných metod pro studium molekulární dynamiky materiálů. Díky nedávnému pokroku v přístrojové a měřicí technice je dnes možné získat dielektrické spektrum v širokém frekvenčním intervalu a pro velice rozdílné materiály. Cílem mé práce bylo studium dielektrických relaxačních spekter a vodivosti oxidů titanu, niobu, tantalu, lanthanu a hafnia pro katody pracující na principu studené emise. Cílem výzkumu bylo analyzovat frekvenční a teplotní chování těchto oxidů, včetně jejich vodivosti, v širokém frekvenčním a teplotním rozsahu, a pokusit se stanovit původ relaxačního mechanismu. Vzhledem k tomu, že původně zadaný rozsah oxidů byl dosti široký, soustředila se pozornost pouze na oxidy tantalu a niobu, rovněž s ohledem na jejich aplikace v elektrolytických kondenzátorech. Elektrické, tepelné a mechanické (při zpracování) vlastnosti oxidů tantalu a niobu jsou dnes již dobře prozkoumány. K dispozici je však jen málo poznatků o jejich dielektrických relaxačních mechanismech. Výsledky získané pro Ta2O5 ukazují existence relaxačního maxima, nacházejícího se v experimentálně dostupném teplotním a frekvenčním intervalu 187 K – 385 K a 1 Hz – 10 MHz. Frekvence ztrátového maxima se řídí Arrheniovým zákonem s aktivační energií 0.048 eV. Ve vodivostních spektrech vykazují tenké vrstvy Ta2O5 na nízkých frekvencích ustálenou hodnotu a při vysokých frekvencích monotónní nárůst, který závisí na teplotě. Pozorovanou vodivost lze popsat mocninnou funkcí s exponentem nepatrně větším než jedna (tzv. superlineární závislost). Výsledky získané pro Nb2O5 v podobné teplotní a frekvenční oblasti, 218 K – 373 K, 1 Hz – 1 MHz rovněž ukazují jedno relaxační maximum. Frekvence ztrátového maxima se opět řídí Arrheniovým zákonem s poněkud vyšší aktivační energií 0.055 eV. Niobové kondenzátory vykazují vodivostní mechanismus shodný s kondenzátory tantalovými.
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Eletrocatalisadores para reação de redução do O2 visando a produção eletroquímica de H2O2: síntese e caracterização de óxidos metálicos nanoestruturados (Ta2O5, MoO3, Nb2O5 ou ZrO2) incorporados em carbono Printex 6L e em grafeno / Electrocatalysts for O2 reduction reaction to H2O2 electrogeneration: synthesis and characterization of nanostructured metal oxides (Ta2O5, MoO3, Nb2O5 ou ZrO2) incorporated into Printex 6L carbon and grapheneCarneiro, Jussara Fernandes 29 October 2015 (has links)
O uso do peróxido de hidrogênio eletrogerado in situ em Processos Oxidativos Avançados (POAs) é um promissor método para o tratamento de efluentes orgânicos. Neste contexto, o desenvolvimento de materiais mais eficientes para viabilizar a reação de redução do oxigênio (RRO) pelo mecanismo envolvendo a transferência de dois elétrons ainda é de grande importância. O presente estudo objetiva a obtenção e a avaliação da atividade catalítica de nanopartículas de óxidos metálicos, Ta2O5, MoO3, Nb2O5 ou ZrO2, incorporadas em carbono Printex 6L e em grafeno no estudo da redução do oxigênio visando a eletrogeração de peróxido de hidrogênio. A caracterização morfológica e microestrutural desses materiais foi investigada por difração de raios X, microscopia eletrônica de transmissão e espectroscopia de fotoelétrons excitados por raios X. O mecanismo da RRO foi analisado pela técnica do eletrodo de disco-anel rotatório. O carbono Printex 6L apresentou uma eficiência de corrente para a eletrogeração de H2O2 (I(H2O2)%) igual a 65,3% em K2SO4 0,1 mol L-1 (pH =2). Após o tratamento térmico desse substrato pelo método dos precursores poliméricos, a eficiência de corrente aumentou 17,1%, ou seja, I(H2O2)% igual a 76,5%. A modificação do carbono Printex 6L com nanopartículas cristalinas de Ta2O5, MoO3, Nb2O5 ou ZrO2 deslocou o potencial de meia-onda para a RRO para valores menos negativos e aumentou a I(H2O2)%. O Nb2O5/C apresentou a maior I(H2O2)%, 87,1%, enquanto o ZrO2/C deslocou o potencial em 137 mV. O estudo comparativo entre três substratos de carbono para a redução do oxigênio, revelou que o óxido de grafeno reduzido apresentou maior atividade para a RRO comparado ao óxido de grafeno e ao carbono Printex 6L, tanto em eletrólito ácido quanto em eletrólito alcalino. A modificação do rGO com Nb2O5 ou ZrO2 pelo método hidrotermal aumentou a atividade catalítica desse substrato para a RRO. A maior eletrogeração de H2O2 foi observada na presença do ZrO2. De fato, um aumento de 73,7% para 88,5% em K2SO4 0,1 mol L-1 (pH =2), e de 72,9% para 83,1% em NaOH 0,1 mol L-1, foi observado em rGO e ZrO2-rGO, respectivamente. Além disso, o ZrO2-rGO apresentou menor sobrepotencial para a RRO comparado ao rGO sem modificador. Portanto, a presença das nanopartículas de óxidos metálicos na matriz condutora de carbono amorfo intensificou a atividade catalítica para a eletrogeração do H2O2, tanto em carbono Printex 6L quanto em óxido de grafeno reduzido, indicando o efeito sinérgico entre as nanopartículas e o subtrato de carbono. Consequentemente, os catalisadores avaliados neste trabalho são promissores para a eletrogeração de espécies oxidantes in situ e sua aplicaçao em POAs. / In situ electrogeneration of hydrogen peroxide has been greatly application in Advanced Oxidation Processes (AOPs) as an effective water treatment technology. In this context, the development of electrode materials that enable the oxygen reduction reaction (ORR) mechanism through a two-electron pathway with high selectivity at low overpotential has a pronounced importance. In the present study, we investigate the properties of Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles supported on Printex 6L carbon and reduced graphene oxide for the electrocatalysis of oxygen reduction to H2O2. The structures and morphologies of these materials were characterized by X-ray diffraction analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Electrochemical activities toward the ORR were evaluated using a rotating ring-disk electrode system. Printex 6L carbon showed a current efficiency for H2O2 production (I(H2O2)%) of 65.3% in K2SO4 0.1 mol L-1 (pH =2) whereas the carbon heat-treated by the polymeric precursor method displayed 76.5% yield of H2O2 electrogeneration. Carbon Printex 6L modified with Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles shifted the half-wave potential for the ORR to less negative potential and increased the I(H2O2)%. The Nb2O5/C showed the highest I(H2O2)%, 87,1%, and the ZrO2/C shifted the potential 137 mV. The comparative study of ORR in acid and alkaline media for the three different conductive carbon pigment showed that the reduced graphene oxide displayed higher activity to oxygen reduction than graphene oxide and Printex 6L carbon. Reduced graphene oxide modified with Nb2O5 or ZrO2 nanoparticles by hydrothermal method increased the catalytic activity of this substrate for ORR which the highest H2O2 electrogeneration was observed for ZrO2-rGO. Indeed, an increase from 73.7% to 88.5% in K2SO4 0.1 mol L-1 (pH =2) and from 72.9% to 83.1% in NaOH 0.1 mol L-1 was obtained for rGO and ZrO2-rGO, respectively. Additionally, the ZrO2-rGO electrocatalyst exhibited overpotential lower than that of rGO unmodified. Therefore, the metallic oxides nanoparticles in both carbon Printex 6L and reduced graphene oxide enhanced the catalytic activity for H2O2 electrogeneration indicating the synergistic effect between the nanoparticles and the amorphous carbon. The catalysts evaluated in this study are promising for in situ electrogeneration of oxidizing agents to be used in the degradation of organic pollutants.
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Eletrocatalisadores para reação de redução do O2 visando a produção eletroquímica de H2O2: síntese e caracterização de óxidos metálicos nanoestruturados (Ta2O5, MoO3, Nb2O5 ou ZrO2) incorporados em carbono Printex 6L e em grafeno / Electrocatalysts for O2 reduction reaction to H2O2 electrogeneration: synthesis and characterization of nanostructured metal oxides (Ta2O5, MoO3, Nb2O5 ou ZrO2) incorporated into Printex 6L carbon and grapheneJussara Fernandes Carneiro 29 October 2015 (has links)
O uso do peróxido de hidrogênio eletrogerado in situ em Processos Oxidativos Avançados (POAs) é um promissor método para o tratamento de efluentes orgânicos. Neste contexto, o desenvolvimento de materiais mais eficientes para viabilizar a reação de redução do oxigênio (RRO) pelo mecanismo envolvendo a transferência de dois elétrons ainda é de grande importância. O presente estudo objetiva a obtenção e a avaliação da atividade catalítica de nanopartículas de óxidos metálicos, Ta2O5, MoO3, Nb2O5 ou ZrO2, incorporadas em carbono Printex 6L e em grafeno no estudo da redução do oxigênio visando a eletrogeração de peróxido de hidrogênio. A caracterização morfológica e microestrutural desses materiais foi investigada por difração de raios X, microscopia eletrônica de transmissão e espectroscopia de fotoelétrons excitados por raios X. O mecanismo da RRO foi analisado pela técnica do eletrodo de disco-anel rotatório. O carbono Printex 6L apresentou uma eficiência de corrente para a eletrogeração de H2O2 (I(H2O2)%) igual a 65,3% em K2SO4 0,1 mol L-1 (pH =2). Após o tratamento térmico desse substrato pelo método dos precursores poliméricos, a eficiência de corrente aumentou 17,1%, ou seja, I(H2O2)% igual a 76,5%. A modificação do carbono Printex 6L com nanopartículas cristalinas de Ta2O5, MoO3, Nb2O5 ou ZrO2 deslocou o potencial de meia-onda para a RRO para valores menos negativos e aumentou a I(H2O2)%. O Nb2O5/C apresentou a maior I(H2O2)%, 87,1%, enquanto o ZrO2/C deslocou o potencial em 137 mV. O estudo comparativo entre três substratos de carbono para a redução do oxigênio, revelou que o óxido de grafeno reduzido apresentou maior atividade para a RRO comparado ao óxido de grafeno e ao carbono Printex 6L, tanto em eletrólito ácido quanto em eletrólito alcalino. A modificação do rGO com Nb2O5 ou ZrO2 pelo método hidrotermal aumentou a atividade catalítica desse substrato para a RRO. A maior eletrogeração de H2O2 foi observada na presença do ZrO2. De fato, um aumento de 73,7% para 88,5% em K2SO4 0,1 mol L-1 (pH =2), e de 72,9% para 83,1% em NaOH 0,1 mol L-1, foi observado em rGO e ZrO2-rGO, respectivamente. Além disso, o ZrO2-rGO apresentou menor sobrepotencial para a RRO comparado ao rGO sem modificador. Portanto, a presença das nanopartículas de óxidos metálicos na matriz condutora de carbono amorfo intensificou a atividade catalítica para a eletrogeração do H2O2, tanto em carbono Printex 6L quanto em óxido de grafeno reduzido, indicando o efeito sinérgico entre as nanopartículas e o subtrato de carbono. Consequentemente, os catalisadores avaliados neste trabalho são promissores para a eletrogeração de espécies oxidantes in situ e sua aplicaçao em POAs. / In situ electrogeneration of hydrogen peroxide has been greatly application in Advanced Oxidation Processes (AOPs) as an effective water treatment technology. In this context, the development of electrode materials that enable the oxygen reduction reaction (ORR) mechanism through a two-electron pathway with high selectivity at low overpotential has a pronounced importance. In the present study, we investigate the properties of Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles supported on Printex 6L carbon and reduced graphene oxide for the electrocatalysis of oxygen reduction to H2O2. The structures and morphologies of these materials were characterized by X-ray diffraction analysis, transmission electron microscopy and X-ray photoelectron spectroscopy. Electrochemical activities toward the ORR were evaluated using a rotating ring-disk electrode system. Printex 6L carbon showed a current efficiency for H2O2 production (I(H2O2)%) of 65.3% in K2SO4 0.1 mol L-1 (pH =2) whereas the carbon heat-treated by the polymeric precursor method displayed 76.5% yield of H2O2 electrogeneration. Carbon Printex 6L modified with Ta2O5, MoO3, Nb2O5 or ZrO2 nanoparticles shifted the half-wave potential for the ORR to less negative potential and increased the I(H2O2)%. The Nb2O5/C showed the highest I(H2O2)%, 87,1%, and the ZrO2/C shifted the potential 137 mV. The comparative study of ORR in acid and alkaline media for the three different conductive carbon pigment showed that the reduced graphene oxide displayed higher activity to oxygen reduction than graphene oxide and Printex 6L carbon. Reduced graphene oxide modified with Nb2O5 or ZrO2 nanoparticles by hydrothermal method increased the catalytic activity of this substrate for ORR which the highest H2O2 electrogeneration was observed for ZrO2-rGO. Indeed, an increase from 73.7% to 88.5% in K2SO4 0.1 mol L-1 (pH =2) and from 72.9% to 83.1% in NaOH 0.1 mol L-1 was obtained for rGO and ZrO2-rGO, respectively. Additionally, the ZrO2-rGO electrocatalyst exhibited overpotential lower than that of rGO unmodified. Therefore, the metallic oxides nanoparticles in both carbon Printex 6L and reduced graphene oxide enhanced the catalytic activity for H2O2 electrogeneration indicating the synergistic effect between the nanoparticles and the amorphous carbon. The catalysts evaluated in this study are promising for in situ electrogeneration of oxidizing agents to be used in the degradation of organic pollutants.
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Zirconium-doped tantalum oxide high-k gate dielectric filmsTewg, Jun-Yen 17 February 2005 (has links)
A new high-k dielectric material, i.e., zirconium-doped tantalum oxide (Zr-doped TaOx), in the form of a sputter-deposited thin film with a thickness range of 5-100 nm, has been studied. Important applications of this new dielectric material include the gate dielectric layer for the next generation metal-oxide-semiconductor field effect transistor (MOSFET). Due to the aggressive device scaling in ultra-large-scale integrated circuitry (ULSI), the ultra-thin conventional gate oxide (SiO2) is unacceptable for many practical reasons. By replacing the SiO2 layer with a high dielectric constant material (high-k), many of the problems can be solved. In this study, a novel high-k dielectric thin film, i.e., TaOx doped with Zr, was deposited and studied. The films electrical, chemical, and structural properties were investigated experimentally. The Zr dopant concentration and the thermal treatment condition were studied with respect to gas composition, pressure, temperature, and annealing time. Interface layer formation and properties were studied with or without an inserted thin tantalum nitride (TaNx) layer. The gate electrode material influence on the dielectric properties was also investigated. Four types of gate materials, i.e., aluminum (Al), molybdenum (Mo), molybdenum nitride (MoN), and tungsten nitride (WN), were used in this study. The films were analyzed with ESCA, XRD, SIMS, and TEM. Films were made into MOS capacitors and characterized using I-V and C-V curves. Many promising results were obtained using this kind of high-k film. It is potentially applicable to future MOS devices.
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